CN108751176A - A kind of preparation method of plating copper nano-particle graphene composite material - Google Patents

A kind of preparation method of plating copper nano-particle graphene composite material Download PDF

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Publication number
CN108751176A
CN108751176A CN201810567610.8A CN201810567610A CN108751176A CN 108751176 A CN108751176 A CN 108751176A CN 201810567610 A CN201810567610 A CN 201810567610A CN 108751176 A CN108751176 A CN 108751176A
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composite material
copper nano
plating copper
mixed solution
graphene composite
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马颖
安博星
戢鸿泽
刘璐
李墨文
任品桥
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Shenyang Jianzhu University
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Shenyang Jianzhu University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Abstract

A kind of preparation method of plating copper nano-particle graphene composite material, belongs to graphene applied technical field；Method is：1) EDTA2Na powder is added to CuSO4It in solution, under the conditions of magnetic agitation, is sufficiently mixed, mixed solution A is made；2) graphene powder is added into mixed solution A, ultrasonic disperse after mixed solution B is made；3) reducing agent is added in mixed solution B, mixed solution C is made；Mixed solution C system is adjusted with NaOH, obtains reddish black plating copper nano-particle graphene composite material precipitation；4) it by reddish black plating copper nano-particle graphene composite material precipitation, filters, cleaning, solid product is dried under vacuum is made plating copper nano-particle graphene composite material.Composite material impurity content prepared by the method for the present invention is low；The copper nano particles grain size adsorbed on the surface of graphene is small, is evenly distributed and the bond strength of graphene is high, improve the electric property of composite material.

Description

A kind of preparation method of plating copper nano-particle graphene composite material
Technical field
The present invention relates to graphene applied technical fields, more particularly to a kind of plating copper nano-particle graphene composite material Preparation method.
Background technology
Since 2004 are found, graphene causes research with its unique crystal structure and excellent physical characteristic The extensive concern of persons.Graphene is by the carbonaceous new material of the tightly packed formation of single layer of carbon atom, is most thin in the world at present Two-dimensional material, thickness only has 0.335nm.This special crystal structure of graphene make it have excellent mechanics, calorifics and Electric property.In addition, graphene also has the specific surface area (2630m of super large2/ g), it is that electric conductivity is best at normal temperatures at present Material.It is wide that these properties of graphene make it be shown in fields such as electronic information, energy new material and war industrys Application prospect.However, since the thickness of graphene is in nanoscale, not surface treated graphene powder would generally occur Mutually reunite to reduce surface energy.And in practical applications, the graphene reunited together can not be formed under macro-scale The conductive network of effect can not be overlapped mutually the membrane structure for constituting densification, and the conductive network formed under macro-scale or densification Membrane structure be graphene macroscopic view application two kinds of principal modes.
Metal nanoparticle is due to its special attribute, in optics, magnetics, calorifics, electronics, photoelectronics, catalysis, letter It is with important application prospects to cease storage, biological standardization, sensing etc..In recent years, by the metal nanoparticle of different function It is assembled by method appropriate, has obtained some multi-functional composite woods with unique electricity, optics, magnetics, mechanical property Material.Unique two-dimensional drape structure and large specific surface area that graphene has become the best load of metal nanoparticle Body.Graphene-supported metal nanoparticle prepares composite material, can not only increase the surface area of metal nanoparticle, enhancing gold Belong to the activity of nano-particle, reduces the loss of metal nanoparticle in the application, and completely new effect can be generated.In addition, Due to the effect of piece interlayer Van der Waals force, graphene has the tendency that irreversible reunion, and the metal being present between graphene layer is received Rice corpuscles just plays the role of the neighbouring graphene sheet layer of separation, prevents to reunite.
Although for the preparation method of graphene-supported metal nano particle composite material, there are reports at present, this The main noble metal nano particles such as including Au, Pt, Ag, Pd of graphene-supported metal nanoparticle in a little reports.And copper conduct A kind of important metallic element, abundance is big, cheap, and copper nano material can be used as the original of high-performance block materials Material.By solution phase chemical reduction, under alkaline condition, copper nano-particle is assembled on the surface of graphene from atomic level, with The control to grain size and pattern is realized, to make gained graphene composite material that there is excellent electrical conduction and heat-conductive characteristic. The preparation method has feature simple for process, convenient, efficient.Graphene-supported copper nano-particle composite material is in nanoelectronic The fields such as, machinery, printed circuit will play a great role.
Invention content
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of plating copper nano-particle graphene composite material. This method is using graphene powder as carrier, with cupric sulfate pentahydrate (CuSO4·5H2O it is) presoma, with ethylenediamine tetra-acetic acid two Sodium salt (EDTA2Na) is used as complexing agent, with formaldehyde (CH2O), sodium borohydride (NaBH4), dimethyamine borane (DMAB) be also Former agent, using sodium hydroxide (NaOH) as pH adjusting agent, using deionized water as solvent, on the surface of graphene with chemical reduction method It plates copper nano-particle and obtains composite material.
A kind of preparation method of plating copper nano-particle graphene composite material of the present invention, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=(0.6~0.95)：1, by EDTA2Na powder be added to CuSO4In aqueous solution, wherein CuSO4The molar concentration of solution is 0.08~0.12mol/L；
(2) under the conditions of magnetic agitation, make EDTA2Na and CuSO4Solution is sufficiently mixed, and mixed solution A is made；
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：(1~16), by graphene powder plus Enter into mixed solution A, mixed solution B is made；
(2) mixed solution B ultrasound sound is disperseed, jitter time is 30~60min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=(10~20)：1, reducing agent is added in mixed solution B, is made Obtain mixed solution C；
(2) at ambient temperature, mixed solution C system is adjusted with NaOH, the color of mixed solution C is made to become from black-and-blue Reddish black is stood, and obtains reddish black plating copper nano-particle graphene composite material precipitation；
Step 4：
(1) it by reddish black plating copper nano-particle graphene composite material precipitation, filters, cleaning；
(2) under vacuum by solid product, at 50 DEG C~70 DEG C, it is multiple to dry obtained plating copper nano-particle graphene Condensation material.
In the step 1 (1), by CuSO4·5H2O is dissolved in deionized water, be made molar concentration be 0.08~ The solution of 0.12mol/L.
In the step 1 (2), the magnetic agitation time is 10~15min.
In the step 2 (1), graphene powder is made by intercalation stripping method.
In the step 2 (2), ultrasonic disperse uses ultrasonic cleaner.
In the step 3 (2), when adding reducing agent, when pH value reaches in 8.0~9.0 and 12.5~13.5 ranges, generate A large amount of bubbles, use ethyl alcohol as antifoaming agent.
In the step 3 (2), time of repose be 5~for 24 hours.
In the step 3 (2), when adjusting mixed solution C system with NaOH, the color of mixed solution C is rapidly from blue-black Color rapidly goes to reddish black.
In the step 3 (2), when using formaldehyde as reducing agent, with NaOH powder adjust the pH value of mixed liquor to 12.5~ 13.5, with sodium borohydride (NaBH4), dimethyamine borane (DMAB) be reducing agent when, use 1mol/L NaOH aqueous solutions adjust The pH value of mixed liquor is to 8.0~9.0.
In the step 4 (1), solid product cleaning uses water and ethyl alcohol.
In the step 4 (1), vacuum drying is carried out using vacuum drying oven, vacuum degree≤100Pa is kept in vacuum drying oven.
In the step 4 (2), drying time is 5~7h.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) copper nano-particle is directly plated on graphene layer, the composite material impurity content of preparation is low, has a wide range of application；
(2) the copper nano particles grain size adsorbed on the surface of graphene is small, is evenly distributed and the bond strength of graphene is high；
(3) copper nano-particle is closely adsorbed on graphene layer, can be played the neighbouring graphene sheet layer of separation, be prevented from sending out The raw effect reunited, and graphene can be used as conductive bridge that copper nano-particle is joined together to form conductive path, carry The electric property of high composite material.
Description of the drawings
Fig. 1 is the plating copper nano-particle graphene composite material table prepared as reducing agent using formaldehyde in the embodiment of the present invention 2 The scanning electron microscope pattern in face；
Fig. 2 is the plating copper nano-particle graphene composite wood prepared as reducing agent using sodium borohydride in the embodiment of the present invention 4 Expect the scanning electron microscope pattern on surface；
Fig. 3 is the plating copper nano-particle graphene composite material table prepared as reducing agent using DMAB in the embodiment of the present invention 9 The scanning electron microscope pattern in face；
Fig. 4 is the plating copper nano-particle graphene composite material prepared as reducing agent using DMAB in the embodiment of the present invention 9 XRD diagram.
Specific implementation mode
Graphene powder is made by intercalation stripping method in following embodiment.
Embodiment 1
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：1,1.536g graphene powders are added
Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min.
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1,37% formaldehyde of reducing agent 13.33mL is added to mixing In solution B, mixed solution C is made.
(2) at ambient temperature, mixed solution C system is adjusted to pH=13.0 with NaOH powder.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 12h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
Embodiment 2
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution, wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：8,0.192g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min.
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1,37% formaldehyde of reducing agent 13.33mL is added to mixing In solution B, mixed solution C is made.
(2) at ambient temperature, mixed solution C system is adjusted to pH=13.0 with NaOH powder.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 12h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
It is as shown in Figure 1 the plating copper nano-particle graphene composite material table prepared by reducing agent of formaldehyde in the present embodiment The scanning electron microscope pattern in face.
Embodiment 3
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：16,0.096g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1,37% formaldehyde of reducing agent 13.33mL is added to mixing In solution B, mixed solution C is made, pH value is adjusted to 13.0 with NaOH powder.
(2) at ambient temperature, mixed solution C system is adjusted to pH=13.0 with NaOH powder.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 12h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
Embodiment 4
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：1,1.536g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1, by reducing agent 18.16g NaBH4It is added dropwise to mixing In solution B, mixed process continues 10min, and mixed solution C is made；
(2) at ambient temperature, with the pH value of 1mol/L NaOH aqueous solution regulation systems to 8.5.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 6h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
It is illustrated in figure 2 the plating copper nano-particle graphene composite wood prepared as reducing agent using sodium borohydride in the present embodiment Expect the scanning electron microscope pattern on surface；
Embodiment 5
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：8,0.192g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1, by reducing agent 18.16g NaBH4It is added dropwise to mixing In solution B, mixed process continues 10min, and mixed solution C is made；
(2) at ambient temperature, with the pH value of 1mol/L NaOH aqueous solution regulation systems to 8.5.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 6h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
Embodiment 6
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：16,0.096g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1, by reducing agent 18.16g NaBH4It is added dropwise to mixing In solution B, mixed process continues 10min, and mixed solution C is made；
(2) at ambient temperature, with the pH value of 1mol/L NaOH aqueous solution regulation systems to 8.5.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 6h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
Embodiment 7
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：1,1.536g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1, reducing agent 28.32g DMAB are added dropwise to mixing In solution B, mixed process continues 10min, and mixed solution C is made；
(2) at ambient temperature, with the pH value of 1mol/L NaOH aqueous solution regulation systems to 8.5.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 6h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
Embodiment 8
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
In mass ratio, graphene powder：Element=1 Cu in mixed solution A：8, by 0.192g graphene powders be added to In mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1, reducing agent 28.32g DMAB are added dropwise to mixing In solution B, mixed process continues 10min, and mixed solution C is made；
(2) at ambient temperature, with the pH value of 1mol/L NaOH aqueous solution regulation systems to 8.5.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 6h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
Embodiment 9
A kind of preparation method of plating copper nano-particle graphene composite material, includes the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=0.82：1, by 7.3g EDTA2Na powder be added to CuSO4In aqueous solution.Wherein CuSO4The molar concentration of solution is 0.12mol/L, by 6g CuSO4·5H2O is dissolved in 200ml and goes In ionized water, the CuSO that molar concentration is 0.12mol/L is made4Solution.
(2) under the conditions of magnetic agitation, make EDTA2Na solution and CuSO4Solution is sufficiently mixed, and mixed solution A is made, The magnetic agitation time is 10min.
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：16,0.096g graphene powders are added Enter into mixed solution A, mixed solution B is made.
(2) mixed solution B is used into ultrasonic cleaner ultrasonic disperse, jitter time 30min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=20：1, reducing agent 28.32g DMAB are added dropwise to mixing In solution B, mixed process continues 10min, and mixed solution C is made；
(2) at ambient temperature, with the pH value of 1mol/L NaOH aqueous solution regulation systems to 8.5.Reaction acutely and with A large amount of bubbles generate, and the beaker inner wall that exists while stirring sprays ethyl alcohol, eliminates a large amount of bubble.Make the color of mixed solution C Become reddish black from black-and-blue, stand 6h, obtains reddish black plating copper nano-particle graphene composite material precipitation.
Step 4：
By reddish black plating copper nano-particle graphene composite material precipitated product filtering, is cleaned, stayed with water and ethyl alcohol in succession The slurry of lower reddish black, is placed in vacuumize in vacuum drying oven and is heated to 60 DEG C, keeps vacuum degree≤100Pa in baking oven, dries 6h It takes out afterwards and obtains plating copper nano-particle graphene composite material.
It is illustrated in figure 3 the plating copper nano-particle graphene composite material table prepared as reducing agent using DMAB in the present embodiment The scanning electron microscope pattern in face；
It is illustrated in figure 4 the plating copper nano-particle graphene composite material prepared as reducing agent using DMAB in the present embodiment XRD diagram.
The invention is not limited in above-mentioned specific embodiment, above-mentioned specific implementation mode is only schematic, and Be not limiting, those skilled in the art under the inspiration of the present invention, without deviating from the spirit of the invention, Many variations can also be made, within these are all belonged to the scope of protection of the present invention.

Claims (10)

1. a kind of preparation method of plating copper nano-particle graphene composite material, which is characterized in that include the following steps：
Step 1：
(1) in molar ratio, EDTA2Na：CuSO4·5H2O=(0.6~0.95)：1, by EDTA2Na powder be added to CuSO4In aqueous solution, wherein CuSO4The molar concentration of solution is 0.08~0.12mol/L；
(2) under the conditions of magnetic agitation, make EDTA2Na and CuSO4Solution is sufficiently mixed, and mixed solution A is made；
Step 2：
(1) in mass ratio, graphene powder：Element=1 Cu in mixed solution A：(1~16), by graphene powder be added to In mixed solution A, mixed solution B is made；
(2) mixed solution B ultrasound sound is disperseed, jitter time is 30~60min；
Step 3：
(1) molar concentration rate, reducing agent are pressed：CuSO4=(10~20)：1, reducing agent is added in mixed solution B, is made mixed Close solution C；
(2) at ambient temperature, mixed solution C system is adjusted with NaOH, the color of mixed solution C is made to become red-black from black-and-blue Color is stood, and obtains reddish black plating copper nano-particle graphene composite material precipitation；
Step 4：
(1) it by reddish black plating copper nano-particle graphene composite material precipitation, filters, cleaning；
(2) under vacuum by solid product, it at 50 DEG C~70 DEG C, dries and plating copper nano-particle graphene composite wood is made Material.
2. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 1 (1), CuSO4·5H2O is dissolved in deionized water, and it is the molten of 0.08~0.12mol/L that molar concentration, which is made, Liquid.
3. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 1 (2), the magnetic agitation time is 10~15min.
4. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 2 (1), graphene powder is made by intercalation stripping method.
5. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 3 (2), when adding reducing agent, when pH value reaches in 8.0~9.0 and 12.5~13.5 ranges, a large amount of gas are generated Bubble, uses ethyl alcohol as antifoaming agent.
6. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 3 (2), time of repose be 5~for 24 hours.
7. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 3 (2), when using formaldehyde as reducing agent, with the pH value of NaOH powder adjusting mixed liquor to 12.5~13.5, with boron Sodium hydride (NaBH4), dimethyamine borane (DMAB) is when being reducing agent, use 1mol/L NaOH aqueous solutions to adjust mixed liquor PH value is to 8.0~9.0.
8. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 4 (1), solid product cleaning uses water and ethyl alcohol.
9. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 4 (1), vacuum drying is carried out using vacuum drying oven, vacuum degree≤100Pa is kept in vacuum drying oven.
10. a kind of preparation method of plating copper nano-particle graphene composite material according to claim 1, it is characterised in that In the step 4 (2), drying time is 5~7h.
CN201810567610.8A 2018-06-05 2018-06-05 A kind of preparation method of plating copper nano-particle graphene composite material Pending CN108751176A (en)

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